Method for making a nanoporous granular material and a detergent composition

ABSTRACT

A process for producing a starting material in a granular form and in a nanoporous anhydrous state, a process for improving the water-solubility and controlled release characteristics of a detergent material, and a detergent composition are disclosed. In one aspect, a process for producing a starting material in a granular form and in a nanoporous anhydrous state includes obtaining a starting material in a form of a dispersion or solution in a sublimable solvent or mixtures of sublimable solvents, forming graded droplets by atomization, freezing the graded droplets in a freezing medium at a controlled freezing rate of a least 100° C. per second to form frozen droplets and drying the frozen droplets by vacuum sublimation to obtain freeze-dried granules of the starting material in a nanoporous anhydrous state. The starting material in dispersion or solution form has a viscosity suitable for atomization and formation of graded droplets.

This application claims the benefit of Application No. 60/104,344 filedOct. 15, 1998.

TECHNICAL FIELD

The present invention relates to nanoporous granular materials, and moreparticularly, to a process for producing a starting material in agranular form and in a nanoporous anhydrous state, a process forimproving the water-solubility and controlled release characteristics ofa detergent material, and a detergent composition.

BACKGROUND OF THE INVENTION

Starting materials in the granular form, such as those used for makingdetergent compositions, have various disadvantages related to the lackof particle size and particle pore size uniformity. One majordisadvantage resulting from granular materials having non-uniform poresize, low porosity and non-uniform size distribution is that thesolubility of the detergent composition in water is detrimentallyaffected. Currently, detergent formulators are faced with numerousproblems which impede delivering the active ingredients to the fabric ordishware to be cleaned. By way of example, recent low dosage or“compact” detergent products experience dissolution problems, especiallyin cold temperature laundering solutions (i.e., less than about 30° C.).More specifically, poor dissolution results in the formation of “clumps”which appear as solid white masses remaining in the washing machine oron the laundered clothes after conventional washing cycles. These“clumps” are especially prevalent under cold temperature washingconditions and/or when the order of addition to the washing machine issuch that the laundry detergent is added first, the clothes are addedthereafter and the water is added in the end, commonly known as the“Reverse Order Of Addition” or “ROOA”. Similarly, this clumpingphenomenon can contribute to the incomplete dispensing of detergent inwashing machines equipped with dispenser drawers or in other dispensingdevices, such as a granulettes. In such cases, the undesired result isundissolved detergent residue in the dispensing device.

Another disadvantage is that non-uniform granular materials fordetergent applicants do not have a high amount of liquid loadingcapability, which is necessary, for example, for loading perfume onto adetergent granule. Also it has been recognized by the inventors of thisinvention that larger pore size and non-uniform pore size distributionin a granular detergent composition leads to lower active agglomerates,i.e., agglomerates that do not have the level of activity desirable fordetergent applications.

Another disadvantage of this particle size non-uniformity in powderedstarting materials is the presence of sometimes significant amounts ofvery fine particles which very frequently lead to safety and healthproblems due to the risk of dusting and pollution by these very fineparticles. Consumers of detergent compositions do not want to be exposedto detergent agglomerates that have these undesirable dustingcharacteristics. Another problem in the detergent area is that thenon-uniform size caused the granular starting materials to generallyflow with difficulty, which makes it difficult to handle them and inparticular, to dose them correctly during usage.

It is very desirable to produce starting materials, such as detergentmaterials, in the form of granules, that is to say, agglomerates ofpowder grains having a regular shape, an even surface, a nanoporoussized porosity, and of a generally graded size. The desirability ofcreating nanoporous sized granular starting materials for laundry andcleaning applications, such as in detergent compositions has beenrecognized by the inventors of this invention and it has been theirfocus to develop a process and product that results in granularmaterials that dissolve easily, are high active agglomerates and thathave high liquid loading capability. It has been recognized that in thenon-detergent applications, these nanoporous sized granules, which areless volatile than particles of powder, exhibit an appreciably reducedrisk of atmospheric pollution and consequently of poisoning byinhalation via the respiratory tract, in the case of toxic startingmaterials. Further, when the starting material is provided in the formof granules having a regular shape, an even surface and a graded size,it can easily be handled, especially owing to ease of flow, and inparticular it is easy to carry out the precise automatic weighingthereof for packaging purposes as well as dosing during subsequent uses.The present invention overcomes the problems, as set forth above.

BACKGROUND ART

Lyophilization is a known technique for obtaining anhydrous productswhich comprises the desiccation, by sublimation, of a product which hasbeen solidified beforehand by freezing. This lyophilization is used forthe manufacture of pharmaceutical, cosmetic, food or veterinary productsin pulverulent form.

Published Japanese Patent Application JP 87 305 829 describes thepreparation of a chitosan powder by dissolving chitosan in an acid,suspending, freezing and lyophilizing in order to obtain chitosangranules. Such a process does not make it possible to obtain granuleswith an even surface and with a homogeneous size, and in the nanoporouspore size range.

Published Japanese Patent Application JP 81 152 449 describes a processfor the production of a fine powder which consists in dissolving avehicle substance in an alcoholic solvent, in spraying the solution inan atmosphere at a temperature of less than −40 degrees C. in order toobtain frozen granulated fines and in drying the granules under vacuumwhile retaining them in the frozen state. Owing to the fact that thegranules are formed by spraying by means of a propellant gas, the flowobtained is in the form of a more or less continuous thin stream and itis not possible to obtain frozen granules of homogeneous size, nor arethey nanoporous.

U.S. Pat. No. 5,611,973 issued to Gurfein et al. on Mar. 18, 1997discloses a process for producing a starting material, and in particularcolouring materials, in the form of anhydrous granules having a regularshape, an even surface and a graded size. This process provides granuleshaving sufficient cohesion for their subsequent uses and providesgranules having a microporous structure which facilitates subsequentdissolution of the product. However, this patent does not provide aprocess for producing nanoporous size granular starting materials thathave markedly improved solubility, activity, liquid loading capabilityand particularly, nanoporous granular materials for detergentapplications.

SUMMARY OF THE INVENTION

The invention meets the needs above by providing a process for producinga starting material in a granular form and in a nanoporous anhydrousstate, a process for improving the water-solubility and controlledrelease characteristics of a detergent material, and a detergentcomposition.

In one aspect of the present invention, a process for producing astarting material in a granular form and in a nanoporous anhydrous stateis disclosed. The process includes the steps of obtaining a startingmaterial in a form of a dispersion or solution in a sublimable solventor mixtures of sublimable solvents, forming graded droplets byatomization, freezing the graded droplets in a freezing medium at acontrolled freezing rate of at least 100° C. per second to form frozendroplets and drying the frozen droplets by vacuum sublimation to obtainfreeze-dried granules of the starting material in a nanoporous anhydrousstate. The starting material in dispersion or solution form has aviscosity suitable for atomization and formation of graded droplets.

In another aspect of the present invention, a process for improvingwater-solubility and controlled release characteristics of a detergentmaterial is disclosed. The process includes the steps of obtaining adetergent starting material in a form of a dispersion or solution in asublimable solvent or mixtures of sublimable solvents, forming gradeddetergent droplets by atomization, freezing the graded detergentdroplets in a freezing medium at a controlled freezing rate of at least100° C. per second to form frozen detergent droplets, and drying thefrozen droplets by vacuum sublimation to obtain freeze-dried detergentgranules of the detergent starting material in a nanoporous anhydrousstate. The detergent starting material in dispersion or solution formhas a viscosity suitable for atomization and formation of gradeddroplets.

In yet another aspect of the present invention, a detergent compositioncomprising freeze-dried detergent granules in a nanoporous anhydrousstate having uniformly sized pores having a pore size less than about300 nanometers is disclosed.

These and other objects, features and attendant advantages of thepresent invention will become apparent to those skilled in the art froma reading of the following detailed description of the preferredembodiment and the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

In the preferred embodiment of the present invention, the process forproducing a starting material in a granular form and in a nanoporousanhydrous state includes the step of obtaining a starting material in aform of a dispersion or solution in a sublimable solvent or mixtures ofsublimable solvents. The starting material can be provided directly inthe form of a solution or of a dispersion in a suitable solvent ormixture of solvents, the viscosity of which can optionally be adjustedby the addition of a chemical agent or by the variation in a physicalparameter, such as the temperature or the concentration of solidmaterial. If the starting material is provided in the form of ananhydrous powder, it is then necessary to prepare a solution ordispersion of this powder in a suitable solvent or mixture of solvents.

The solutions or dispersions of the starting material used in theprocess according to the invention are obtained simply by dissolving ordispersing the powder in a solvent or mixture of solvents suitable forlyophilization. Suitable solvents for lyophilization include water,isopentane, dimethyl sulphoxide, methylamine, ethylamine, diethylamine,propylamine, fumaric acid, acetic acid, t-butyl alcohol, t-amyl alcohol,1,4-dioxane, isobutane, ethylene oxide and cyclohexane. Water is thepreferred sublimable solvent.

The solutions and dispersions used in the process of the invention musthave a viscosity such that they can be formed into graded droplets byatomization. The atomization can be accomplished by ultrasonic,acoustic, electrostatic means, pressure swirl nozzles or two-fluidnozzles, the preferred mode being ultrasonic atomization.

Consequently, the starting material in the form of dispersion orsolution has a viscosity desirably in a range of from about 1 cP toabout 250 cP at a solution temperature in a range of from about 60° C.to about 91° C. and at a shear rate in a range of from about 1000 sec⁻¹to about 10000 sec⁻¹, preferably in a range of from about 25 cP to about125 cP and more preferably in a range of from about 50 cP to about 100cP. The term “solution temperature” means the temperature of thesolution or dispersion of the starting material.

In the preferred embodiment, a structuring agent is added to thestarting material in dispersion or solution to affect crystal growthformation in the graded droplets during the step of freezing. Mentionmay be made, among the structuring agents which can be used in thesolutions or dispersions according to the invention, of mannitol,glucose, lactose, maltose, polyethylene glycol, starch,polyvinylpyrrolidone, inorganic salts, sorbitol and CARBOPOL™ brandcarboxyvinyl polymer (Goodrich Chemical Co.). The choice of thestructuring aid will very clearly depend on the subsequent use envisagedfor the granules. The amount of additives can be easily determined by aperson skilled in the art and depends on the additive.

In the preferred embodiment of the present invention, the startingmaterial in dispersion or solution form has a viscosity suitable foratomization and formation of graded droplets. It is sometimes necessaryto add one or a number of additives in order to obtain theaforementioned viscosity which makes it possible mechanically to formgraded droplets by atomization and/or to confer a certain cohesion ordegree of binding on the resultant granules. These additives aregenerally chosen from the gelling agents known in lyophilization.Suitable gelling agents which can be used in the solutions ordispersions according to the invention, include carbomers, hydroxyethylcellulose, carboxymethyl cellulose, agar, xanthan gum, starch,polyethylene glycol, polyvinylpyrrolidone, locust bean gum, guar gum,gelatin, casein, pectin, alginates and carrageenates. It is alsopossible to adjust the viscosity of the solution or of the dispersion byadjusting the temperature of the solution or of the dispersion duringthe atomization step or even by adjusting the percentage of solids inthe solution or in the dispersion.

In the preferred embodiment of the present invention, the process forproducing a starting material in a granular form and in a nanoporousanhydrous state includes the step of forming graded droplets byatomization. A significant aspect of the process of the presentinvention relates to the formation of drops of graded size from thesolution or dispersion of the starting material. This stage is amechanical shaping stage which, in contrast to other techniques such asspraying or manifold of pipes or needles for droplet formation, makes itpossible to obtain drops with a well-defined generally spherical orsemi-spherical, shape, an even surface and a finely graded size. Byusing atomization techniques, such as by ultrasonic, acoustic,electrostatic, pressure swirl nozzle or two-fluid nozzle means, thepreferred mode being ultrasonic atomization, it is possible to formgraded droplets which have a uniform shape and size. Desirably, thegraded droplets have a uniform spherical shape and a size in a rangefrom about 10 μm to about 700 μm, and preferably they have a uniformspherical shape and a size in a range from about 20 μm to about 100 μm.The drops formed can comprise starting materials of different chemicalnatures and thus form a starting material in the form of granules havingthe characteristics of each of the starting materials.

In the preferred embodiment of the present invention, the process forproducing a starting material in a granular form and in a nanoporousanhydrous state includes the step of freezing the graded droplets in afreezing medium at a controlled freezing rate of desirably at least 100°C. per second to form frozen droplets. Preferably, the controlledfreezing rate is at least 200° C. per second, and more preferably, thecontrolled freezing rate is at least 400° C. per second. The inventorshave discovered that this step is the most critical step to achievingnanoporous sized granular starting materials, i.e., the carefullycontrolled and preselected rate of cooling. Without being bound to anyspecific theory, it is believed that at cooling rates of at least 100°C. per second, the water which usually forms ice-crystals at lowfreezing rates, such as rates less than about 100° C. per second, noweither forms very small crystals, or becomes frozen in its glassy state.As a result of this first phenomenon, when water is sublimed from thefrozen matrix in a vacuum oven, a highly porous matrix is left behindwith pores of a size similar to those of the frozen water pockets thatare formed during the freezing process. These pores are not only smalland nanometer sized, but also have a very homogeneous size distribution.In the preferred embodiment of the present invention, the freeze-driedgranules in a nanoporous anhydrous state have uniformly sized poreshaving a pore size less than about 300 nanometers.

Without being bound to any specific theory, it is believed by theinventors that any salts that are soluble in water and that crystallizeout of the solution during freezing, form either micron or submicron,and more particularly, nanometer sized crystals during the fast rates offreezing, such as rates of at least 100° C. per second. As a result ofthis second phenomenon, when the water is sublimed from the frozenmatrix, a nanometer sized crystalline agglomerate having a sizesubstantially equal to the original droplet size is formed. Theinventors believe that it these two phenomena that lead to a highlyporous matrix with nanometer sized pores within and on the agglomeratesurface.

In the preferred embodiment of the present invention, the process forproducing a starting material in a granular form and in a nanoporousanhydrous state includes the step of drying the frozen droplets byvacuum sublimation to obtain freeze-dried granules of the startingmaterial in a nanoporous anhydrous state.

In another embodiment of the present invention, a process for improvingwater-solubility and controlled release characteristics of a detergentmaterial includes the steps of obtaining a detergent starting materialin a form of a dispersion or solution in a sublimable solvent ormixtures of sublimable solvents, forming graded detergent droplets byatomization, freezing the graded detergent droplets in a freezing mediumat a controlled freezing rate of at least 100° C. per second to formfrozen detergent droplets, and drying the frozen droplets by vacuumsublimation to obtain freeze-dried detergent granules of the detergentstarting material in a nanoporous anhydrous state. The detergentstarting material in dispersion or solution form has a viscositysuitable for atomization and formation of graded droplets. Desirably,the detergent starting material in the form of dispersion or solutionhas a viscosity in a range of from about 50 cP to about 125 cP at asolution temperature in a range of from about 60° C. to about 91° C. andat a shear rate in a range of from about 1000 sec⁻¹ to about 10000sec⁻¹. Desirably, the graded detergent droplets have a uniform sphericalshape and a size in a range from about 20 μm to about 50 μm and formedby atomization, preferably, by ultrasonic atomization means. In thisembodiment, the controlled freezing rate is at least 200° C. per secondand the freeze-dried detergent granules in a nanoporous anhydrous statehave uniformly sized pores having a pore size less than about 300nanometers.

In another preferred embodiment of the present invention, a detergentcomposition comprising freeze-dried detergent granules in a nanoporousanhydrous state having uniformly sized pores having a pore size lessthan about 300 nanometers is disclosed.

Detergent Components

The detergent composition may include surfactant systems such asanionic, nonionic, zwitterionic, ampholytic and cationic surfactantclasses and compatible mixtures thereof. Detergent surfactants aredescribed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, andin U.S. Pat. No. 3,919,678, Laughlin et al., issued Dec. 30, 1975, bothof which are incorporated herein by reference. Cationic surfactantsinclude those described in U.S. Pat. No. 4,222,905, Cockrell, issuedSep. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy, issued Dec. 16,1980, both of which are also incorporated herein by reference.

Nonlimiting examples of surfactant systems include the conventionalC₁₁-C₁₈ alkyl benzene sulfonates (“LAS”) and primary, branched-chain andrandom C₁₀-C₂₀ alkyl sulfates (“AS”), the C₁₀-C₁₈ secondary (2,3)alkylsulfates of the formula CH₃(CH₂)_(x)(CHOSO₃ ⁻M⁺)CH₃ andCH₃(CH₂)_(y)(CHOSO₃ ⁻M⁺)CH₂CH₃ where x and (y+1) are integers of atleast about 7, preferably at least about 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀-C₁₈ alkyl alkoxy sulfates (“AE_(x)S”;especially EO 1-7 ethoxy sulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates(especially the EO 1-5 ethoxycarboxylates), the C₁₀-C₁₈ glycerol ethers,the C₁₀-C₁₈ alkyl polyglycosides and their corresponding sulfatedpolyglycosides, and C₁₂-C₁₈ alpha-sulfonated fatty acid esters. Ifdesired, the conventional nonionic and amphoteric surfactants such asthe C₁₂-C₁₈ alkyl ethoxylates (“AE”) including the so-called narrowpeaked alkyl ethoxylates and C₆-C₁₂ alkyl phenol alkoxylates (especiallyethoxylates and mixed ethoxy/propoxy), C₁₂-C₁₈ betaines andsulfobetaines (“sultaines”), C₁₀-C₁₈ amine oxides, and the like, canalso be included in the surfactant system. The C₁₀-C₁₈ N-alkylpolyhydroxy fatty acid amides can also be used. Typical examples includethe C₁₂-C₁₈ N-methylglucamides. See WO 9,206,154. Other sugar-derivedsurfactants include the N-alkoxy polyhydroxy fatty acid amides, such asC₁₀-C₁₈ N-(3-methoxypropyl) glucamide. The N-propyl through N-hexylC₁₂-C₁₈ glucamides can be used for low sudsing. C₁₀-C₂₀ conventionalsoaps may also be used. If high sudsing is desired, the branched-chainC₁₀-C₁₆ soaps may be used. Mixtures of anionic and nonionic surfactantsare especially useful. Other conventional useful surfactants are listedin standard texts.

The detergent composition can, and preferably does, include a detergentbuilder. Builders are generally selected from the various water-soluble,alkali metal, ammonium or substituted ammonium phosphates,polyphosphates, phosphonates, polyphosphonates, carbonates, silicates,borates, polyhydroxy sulfonates, polyacetates, carboxylates, andpolycarboxylates. Preferred are the alkali metal, especially sodium,salts of the above. Preferred for use herein are the phosphates,carbonates, silicates, C₁₀₋₁₈ fatty acids, polycarboxylates, andmixtures thereof. More preferred are sodium tripolyphosphate,tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates,sodium silicate, and mixtures thereof (see below).

Specific examples of inorganic phosphate builders are sodium andpotassium tripolyphosphate, pyrophosphate, polymeric metaphosphatehaving a degree of polymerization of from about 6 to 21, andorthophosphates. Examples of polyphosphonate builders are the sodium andpotassium salts of ethylene diphosphonic acid, the sodium and potassiumsalts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium andpotassium salts of ethane, 1,1,2-triphosphonic acid. Other phosphorusbuilder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030;3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which areincorporated herein by reference.

Examples of nonphosphorus, inorganic builders are sodium and potassiumcarbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, andsilicates having a weight ratio of SiO₂ to alkali metal oxide of fromabout 0.5 to about 4.0, preferably from about 1.0 to about 2.4.Water-soluble, nonphosphorus organic builders useful herein include thevarious alkali metal, ammonium and substituted ammonium polyacetates,carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples ofpolyacetate and polycarboxylate builders are the sodium, potassium,lithium, ammonium and substituted ammonium salts of ethylene diaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melliticacid, benzene polycarboxylic acids, and citric acid.

Polymeric polycarboxylate builders are set forth in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967, the disclosure of which isincorporated herein by reference. Such materials include thewater-soluble salts of homo- and copolymers of aliphatic carboxylicacids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid,aconitic acid, citraconic acid and methylenemalonic acid. Some of thesematerials are useful as the water-soluble anionic polymer as hereinafterdescribed, but only if in intimate admixture with the nonsoap anionicsurfactant.

Other suitable polycarboxylates for use herein are the polyacetalcarboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979to Crutchfield et al., and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979to Crutchfield et al., both of which are incorporated herein byreference. These polyacetal carboxylates can be prepared by bringingtogether under polymerization conditions an ester of glyoxylic acid anda polymerization initiator. The resulting polyacetal carboxylate esteris then attached to chemically stable end groups to stabilize thepolyacetal carboxylate against rapid depolymerization in alkalinesolution, converted to the corresponding salt, and added to a detergentcomposition. Particularly preferred polycarboxylate builders are theether carboxylate builder compositions comprising a combination oftartrate monosuccinate and tartrate disuccinate described in U.S. Pat.No. 4,663,071, Bush et al., issued May 5, 1987, the disclosure of whichis incorporated herein by reference.

Water-soluble silicate solids represented by the formula SiO₂.M₂O, Mbeing an alkali metal, and having a SiO₂:M₂O weight ratio of from about0.5 to about 4.0, are useful salts in the detergent granules of theinvention at levels of from about 2% to about 15% on an anhydrous weightbasis, preferably from about 3% to about 8%. Anhydrous or hydratedparticulate silicate can be utilized, as well.

Any number of additional ingredients can also be included as componentsin the granular detergent composition. These include other detergencybuilders, bleaches, bleach activators, suds boosters or sudssuppressors, anti-tarnish and anti-corrosion agents, soil suspendingagents, soil release agents, germicides, pH adjusting agents, nonbuilderalkalinity sources, chelating agents, smectite clays, enzymes,enzyme-stabilizing agents and perfumes. See U.S. Pat. No. 3,936,537,issued Feb. 3, 1976 to Baskerville, Jr. et al., incorporated herein byreference.

Bleaching agents and activators are described in U.S. Pat. No.4,412,934, Chung et al., issued Nov. 1, 1983, and in U.S. Pat. No.4,483,781, Hartman, issued Nov. 20, 1984, both of which are incorporatedherein by reference. Chelating agents are also described in U.S. Pat.No. 4,663,071, Bush et al., from Column 17, line 54 through Column 18,line 68, incorporated herein by reference. Suds modifiers are alsooptional ingredients and are described in U.S. Pat. No. 3,933,672,issued Jan. 20, 1976 to Bartoletta et al., and U.S. Pat. No. 4,136,045,issued Jan. 23, 1979 to Gault et al., both incorporated herein byreference.

Suitable smectite clays for use herein are described in U.S. Pat. No.4,762,645, Tucker et al., issued Aug. 9, 1988, Column 6, line 3 throughColumn 7, line 24, incorporated herein by reference. Suitable additionaldetergency builders for use herein are enumerated in the Baskervillepatent, Column 13, line 54 through Column 16, line 16, and in U.S. Pat.No. 4,663,071, Bush et al., issued May 5, 1987, both incorporated hereinby reference.

The following examples are presented for illustrative purposes only andare not to be construed as limiting the scope of the appended claims inany way.

ABBREVIATIONS USED IN EXAMPLES

In the detergent compositions, the abbreviated component identificationshave the following meanings:

LAS: Sodium linear C11-13 alkyl benzene sulfonate

TAS: Sodium tallow alkyl sulfate

CxyAS: Sodium C1x-C1y alkyl sulfate

C46SAS: Sodium C14-C16 secondary (2,3)alkyl sulfate

CxyEzS: Sodium C1x-C1y alkyl sulfate condensed with z moles of ethyleneoxide

CxyEz: C1x-C1y predominantly linear primary alcohol condensed with anaverage of z moles of ethylene oxide

QAS: R2.N+(CH3)2(C2H4OH) with R2=C12-C14

QAS 1: R2.N+(CH3)2(C2H4OH) with R2=C8-C11

APA: C8-C10 amido propyl dimethyl amine

Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture oftallow and coconut fatty acids

STS: Sodium toluene sulphonate

CFAA: C12-C14 (coco)alkyl N-methyl glucamide

TFAA: C16-C18 alkyl N-methyl glucamide

TPKFA: C12-C14 topped whole cut fatty acids

STPP: Anhydrous sodium tripolyphosphate

TSPP: Tetrasodium pyrophosphate

Zeolite A: Hydrated sodium aluminosilicate of formulaNa12(A1O2SiO2)12.27H2O having a primary particle size in the range from0.1 to 10 micrometers (weight expressed on an anhydrous basis)

NaSKS-6: Crystalline layered silicate of formula d-Na2Si2O5

Citric acid: Anhydrous citric acid

Borate: Sodium borate

Carbonate: Anydrous sodium carbonate with a particle size between 200 μmand 900 μm

Bicarbonate: Anhydrous sodium bicarbonate with a particle sizedistribution between 400 μm and 1200 μm

Silicate: Amorphous sodium silicate (SiO2:Na2O=2.0:1)

Sulfate: Anhydrous sodium sulfate

Mg sulfate: Anhydrous magnesium sulfate

Citrate: Tri-sodium citrate dihydrate of activity 86.4% with a particlesize distribution between 425 μm and 850 μm

MA/AA: Copolymer of 1:4 maleic/acrylic acid, average molecular weightabout 70,000

MA/AA (1): Copolymer of 4:6 maleic/acrylic acid, average molecularweight about 10,000

AA: Sodium polyacrylate polymer of average molecular weight 4,500

CMC: Sodium carboxymethyl cellulose

Cellulose ether: Methyl cellulose ether with a degree of polymerizationof 650 available from Shin Etsu Chemicals

Protease: Proteolytic enzyme, having 3.3% by weight of active enzyme,sold by NOVO Industries A/S under the tradename Savinase

Protease I: Proteolytic enzyme, having 4% by weight of active enzyme, asdescribed in WO 95/10591, sold by Genencor Int. Inc.

Alcalase: Proteolytic enzyme, having 5.3% by weight of active enzyme,sold by NOVO Industries A/S

Cellulase: Cellulytic enzyme, having 0.23% by weight of active enzyme,sold by NOVO Industries A/S under the tradename Carezyme

Amylase: Amylolytic enzyme, having 1.6% by weight of active enzyme, soldby NOVO Industries A/S under the tradename Termamyl 120T

Lipase: Lipolytic enzyme, having 2.0% by weight of active enzyme, soldby NOVO Industries A/S under the tradename Lipolase

Lipase (1): Lipolytic enzyme, having 2.0% by weight of active enzyme,sold by NOVO Industries A/S under the tradename Lipolase Ultra

Endolase: Endoglucanase enzyme, having 1.5% by weight of active enzyme,sold by NOVO Industries A/S

PB4: Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2—

PB1: Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O2

Percarbonate: Sodium percarbonate of nominal formula 2Na2CO3.3H2O2

NOBS: Nonanoyloxybenzene sulfonate in the form of the sodium salt

NAC-OBS: (6-nonamidocaproyl)oxybenzene sulfonate

TAED: Tetraacetylethylenediamine

DTPA: Diethylene triamine pentaacetic acid

DTPMP: Diethylene triamine penta(methylene phosphonate), marketed byMonsanto under the Tradename Dequest 2060

EDDS: Ethylenediamine-N,N′-disuccinic acid, (S,S) isomer in the form ofits sodium salt.

Photoactivated: Sulfonated zinc phthlocyanine encapsulated in bleach (1)dextrin soluble polymer

Photoactivated: Sulfonated alumino phthlocyanine encapsulated in bleach(2) dextrin soluble polymer

Brightener 1: Disodium 4,4′-bis(2-sulphostyryl)biphenyl

Brightener 2: Disodium4,4′-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino)stilbene-2:2′-disulfonate

HEDP: 1,1-hydroxyethane diphosphonic acid

PEGx: Polyethylene glycol, with a molecular weight of x (typically4,000)

PEO: Polyethylene oxide, with an average molecular weight of 50,000

TEPAE: Tetraethylenepentaamine ethoxylate

PVI: Polyvinyl imidosole, with an average molecular weight of 20,000

PVP: Polyvinylpyrolidone polymer, with an average molecular weight of60,000

PVNO: Polyvinylpyridine N-oxide polymer, with an average molecularweight of 50,000

PVPVI: Copolymer of polyvinylpyrolidone and vinylimidazole, with anaverage molecular weight of 20,000

QEA: bis((C2H5O)(C2H4O)n)(CH3)—N+—C6H12—N+—(CH3) bis((C2H5O)—(C2H4O))n,wherein n=from 20 to 30

SRP 1: Anionically end capped poly esters

SRP 2: Diethoxylated poly(1,2 propylene terephtalate) short blockpolymer

PEI: Polyethyleneimine with an average molecular weight of 1800 and anaverage ethoxylation degree of 7 ethyleneoxy residues per nitrogen

Silicone antifoam: Polydimethylsiloxane foam controller withsiloxane-oxyalkylene copolymer as dispersing agent with a ratio of saidfoam controller to said dispersing agent of 10:1 to 100:1

Opacifier: Water based monostyrene latex mixture, sold by BASFAktiengesellschaft under the tradename Lytron 621

Wax: Paraffin wax

In the following examples all levels are quoted as % by weight of thecomposition:

EXAMPLE I

The following compositions are in accordance with the invention.

A B C D E F G H I Spray-dried Granules LAS 10.0  10.0  15.0  5.0 5.010.0  — — — TAS — 1.0 — — — — MBAS — — 5.0 5.0 — — — C₄₅AS — — 1.0 2.02.0 — — — C₄₅AE₃S — — 1.0 — — — QAS 1.0 1.0 — — — DTPA, HEDP and/or EDDS0.3 0.3 0.5 0.3 — — — MgSO4 0.5 0.5 0.1 — — — — Sodium citrate — — — 3.05.0 — — — Sodium carbonate 10.0  7.0 15.0  10.0  — — Sodium sulphate 5.05.0 — — 5.0 3.0 — — — Sodium silicate 1.6R — — — — 2.0 — — — Zeolite A16.0  18.0  20.0  20.0  — — — — — SKS-6 — — — 3.0 5.0 — — — — MA/AA orAA 1.0 2.0 11.0  — — 2.0 — — — PEG 4000 — 2.0 — 1.0 — 1.0 — — — QEA 1.0— — — 1.0 — — — — Brightener  0.05  0.05  0.05 —  0.05 — — — — Siliconeoil  0.01  0.01  0.01 — —  0.01 — — — Agglomerate LAS — — — — 2.0 2.0 —MBAS — — — — — — 1.0 C₄₅AS — — — — 2.0 — — AE₃ — — — — — 1.0 0.5Carbonate — — 4.0 1.0 1.0 1.0 — Sodium citrate — — — — — — 5.0 CFAA — —— — — Citric acid — — — 4.0 — 1.0 1.0 QEA — — — 2.0 2.0 1.0 — SRP — — —1.0 1.0 0.2 — Zeolite A — — — 15.0  26.0  15.0  16.0  Sodium silicate —— — — — — — PEG — — — — — — 4.0 — — Builder Agglomerates SKS-6 6.0 — — —6.0 3.0 — 7.0 10.0  LAS 4.0 5.0 — — 5.0 3.0 — 10.0  12.0  Dry-addparticulate components Maleic acid/carbonate/bicarbonate 8.0 10.0  10.0 4.0 — 8.0 2.0 2.0 4.0 (40:20:40) QEA — — — 0.2 0.5 — — — — NACAOBS 3.0 —— 1.5 — — — 2.5 — NOBS — 3.0 3.0 — — — — — 5.0 TAED 2.5 — — 1.5 2.5 6.5— 1.5 — MBAS — — — 8.0 — — 8.0 — 4.0 LAS (flake) 10.0  10.0  — — — — —8.0 — Spray-on Brightener 0.2 0.2 0.3 0.1 0.2 0.1 — 0.6 — Dye — — — 0.3 0.05 0.1 — — — AE7 — — — — — 0.5 — 0.7 — Perfume — — — 0.8 — 0.5 — 0.5— Dry-add Citrate — — 20.0  4.0 — 5.0 15.0  — 5.0 Percarbonate 15.0  3.06.0 10.0  — — — 18.0  5.0 Perborate — — — — 6.0 18.0  — — — Photobleach 0.02  0.02  0.02 0.1  0.05 — 0.3 —  0.03 Enzymes 1.3 0.3 0.5 0.5 0.82.0 0.5  0.16 0.2 (cellulase, amylase, protease, lipase) Carbonate 0.010.0  — — — 5.0 8.0 10.0  5.0 Perfume (encapsulated) 0.6 0.5 0.5 — 0.30.5 0.2 0.1 0.6 Suds suppressor 1.0 0.6 0.3 —  0.10 0.5 1.0 0.3 1.2 Soap0.5 0.2 0.3 3.0 0.5 — — 0.3 — Citric acid — — — 6.0 6.0 — — — 5.0 Dyedcarbonate (blue, green) 0.5 0.5 1.0 2.0 — 0.5 0.5 0.5 1.0 SKS-6 — — —4.0 — — — 6.0 — Fillers up to 100%

EXAMPLE II

The following compositions are in accordance with the invention.

A B C D E F G H I Spray-dried Granules LAS 10.0  10.0  16.0  5.0 5.010.0  — — — TAS — 1.0 — — — — MBAS — — — 5.0 5.0 — — — C₄₅AS — — 1.0 2.02.0 — — — C₄₅AE₃S — — — 1.0 — — — QAS — — 1.0 1.0 — — — DTPA, HEDPand/or EDDS 0.3 0.3 0.3 0.3 — — — MgSO4 0.5 0.4 0.1 — — — — Sodiumcitrate 10.0  12.0  17.0  3.0 5.0 — — — Sodium carbonate 15.0  8.0 15.0 10.0  — — — Sodium sulphate 5.0 5.0 — — 5.0 3.0 — — — Sodium silicate1.6R — — — — 2.0 — — — Zeolite A — — — 2.0 — — — — — SKS-6 — — — 3.0 5.0— — — — MA/AA or AA 1.0 2.0 10.0  — — 2.0 — — — PEG 4000 — 2.0 — 1.0 —1.0 — — — QEA 1.0 — — — 1.0 — — — — Brightener  0.05  0.05  0.05 —  0.05— — — — Silicone oil  0.01  0.01  0.01 — —  0.01 — — — Agglomerate LAS —— — — — — 2.0 2.0 — MBAS — — — — — — — — 1.0 C₄₅AS — — — — — — 2.0 — —AE₃ — — — — — — — 1.0 0.5 Carbonate — — — — 4.0 1.0 1.0 1.0 — Sodiumcitrate — — — — — — — — 5.0 CFAA — — — — — — — — Citric acid — — — — —4.0 — 1.0 1.0 QEA — — — — — 2.0 2.0 1.0 — SRP — — — — — 1.0 1.0 0.2 —Zeolite A — — — — — 15.0  26.0  15.0  16.0  Sodium silicate — — — — — —— — — PEG — — — — — — 4.0 — — Builder Agglomerates SKS-6 6.0 5.0 — — 6.03.0 — 7.0 10.0  LAS 4.0 5.0 — — 5.0 3.0 — 10.0  12.0  Dry-addparticulate components Maleic acid/carbonate/bicarbonate 8.0 10.0  4.04.0 — 8.0 2.0 2.0 4.0 (40:20:40) QEA — — — 0.2 0.5 — — — — NACAOBS 3.0 —— 1.5 — — — 2.5 — NOBS — 3.0 3.0 — — — — — 5.0 TAED 2.5 — — 1.5 2.5 6.5— 1.5 — MBAS — — — 8.0 — — 8.0 — 4.0 LAS (flake) — — — — — — — 8.0 —Spray-on Brightener 0.2 0.2 0.3 0.1 0.2 0.1 — 0.6 — Dye — — — 0.3  0.050.1 — — — AE7 — — — — — 0.5 — 0.7 — Perfume — — — 0.8 — 0.5 — 0.5 —Dry-add Citrate 4.0 — 3.0 4.0 — 5.0 15.0  — 5.0 Percarbonate 15.0  3.06.0 10.0  — — — 18.0  5.0 Perborate — — — — 6.0 18.0  — — — Photobleach 0.02  0.02  0.02 0.1  0.05 — 0.3 —  0.03 Enzymes 1.5 0.3 0.5 0.5 0.82.0 0.5  0.16 0.2 (cellulase, amylase, protease, lipase) Carbonate — — —— — 5.0 8.0 10.0  5.0 Perfume (encapsulated) 0.6 0.5 0.5 — 0.3 0.5 0.20.1 0.6 Suds suppressor 1.0 0.6 0.3 —  0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.20.3 3.0 0.5 — — 0.3 — Citric acid — — — 6.0 6.0 — — — 5.0 Dyed carbonate(blue, green) 0.5 0.5 ? 2.0 — 0.5 0.5 0.5 1.0 SKS-6 — — — 4.0 — — — 6.0— Fillers up to 100%

The following Examples illustrate the benefits of a nanoporousparticulate starting material for making, amongst other products,detergents.

EXAMPLE III

An aqueous solution having the formula set forth in Table A below washeated to a temperature of about 91° C. The solution was then sprayedthrough an ultrasonic atomizer (Sono-Tek®) at a flow rate of 75.3 g/minfor 12 sec at 2.5 watts into a sample tray holding liquid nitrogen. Thefrozen liquid droplets were then lyophilized in a vacuum chamber(commercially available from APS Inc., Model D) under a pressure of 200mTorr for two hours.

TABLE A Component % by Weight MgSO4 27.8 Micronised Carbonate 32.7Distilled Water 49.5

The granules obtained have a spherical shape, a surface area of about 25m²/gm and a porosity of about 28% and exhibit excellent liquid holdingcharacteristics.

EXAMPLE IV

An aqueous solution having the formula set forth in Table B below washeated up to a temperature of about 60° C. The solution was then sprayedthrough an ultrasonic atomizer (Sono-Tek®) at a flow rate of 46 g/minfor 10 sec at 5.0 watts into a sample tray holding liquid nitrogen. Thefrozen liquid droplets were then lyophilized in a vacuum chamber(commercially available from APS inc., Model D) under a pressure of 200mTorr for two hours.

TABLE B Component % by Weight Aluminosilicate 17.5  Sodium Sulfate 4.4Acrylic Acid/Maleic Acid Co-polymer 2.9 C12-13 linear alkylbenzenesulfonate, Na 5.9 Sodium silicate 2.2 Carboxymethylcellulose 0.8Brightener 47 0.2 Silicone antifoam 0.7 DTPMPA¹ 0.4 Water 65.0 ¹Diethylene Triamine Pentamethylenephosphonic Acid

The granules obtained have a spherical shape, a surface area of about 25m²/gm, a porosity of about 30% and exhibit excellent solubilitycharacteristics.

EXAMPLE V

An aqueous solution having 25% by weight of NaCl was heated up to atemperature of about 68° C. The solution was then sprayed through anultrasonic atomizer (Sono-Tek®) at a flow rate of 66.4 g/min for 10 secat 2.5 watts into a sample tray holding liquid nitrogen. The frozenliquid droplets were then lyophilized in a vacuum chamber (commerciallyavailable from APS Inc., Model D) under a pressure of 200 mTorr for twohours.

The granules obtained had a spherical shape, a surface area of about 22m²/gm and a porosity of about 35% and exhibit excellent solubilitycharacteristics.

Accordingly, having thus described the invention in detail, it will beobvious to those skilled in the art that various changes may be madewithout departing from the scope of the invention and the invention isnot to be considered limited to what is described in the specification.

What is claimed is:
 1. A process for producing a starting material for adetergent composition, said starting material being in a granular formand in a nanoporous anhydrous state, comprising the steps of: (a)obtaining a starting material for a detergent composition in a form of adispersion or solution in a sublimable solvent or mixtures of sublimablesolvents, said starting material in dispersion or solution form having aviscosity suitable for atomization and formation of graded droplets; (b)forming graded droplets by atomization; (c) freezing said gradeddroplets in a freezing medium at a controlled freezing rate of at least100° C. per second to form frozen droplets; (d) drying said frozendroplets by vacuum sublimation to obtain freeze-dried granules of saidstarting material in a nanoporous anhydrous state; and (e) loadingperfumes on to said granules.
 2. The process according to claim 1wherein said starting material in the form of dispersion or solution hasa viscosity in a range of from about 1 cP to about 250 cP at a solutiontemperature in a range of from about 60° C. to about 91° C. and at ashear rate in a range of from about 1000 sec⁻¹ to about 10000 sec⁻¹. 3.The process according to claim 2, wherein said starting material in theform of dispersion or solution has a viscosity in a range of from about25 cP to about 125 cP at a solution temperature in a range of from about60° C. to about 91° C. and at a shear rate in a range of from about 1000sec⁻¹ to about 10000 sec⁻¹.
 4. The process according to claim 3, whereinsaid starting material in the form of dispersion or solution has aviscosity in a range of from about 50 cP to about 100 cP at a solutiontemperature in a range of from about 60° C. to about 91° C. and at ashear rate in a range of from about 1000 sec⁻¹ to about 10000 sec⁻¹. 5.The process according to claim 1 wherein a structuring agent is added tosaid starting material in dispersion or solution to affect crystalgrowth formation in said graded droplets during the step of freezing. 6.The process according to claim 5 wherein said structuring agent isselected from the group consisting of mannitol, maltose, glucose,lactose, polyethylene glycol, starch, polyvinylpyrrolidone, inorganicsalts, sorbitol and carboxyvinyl polymer.
 7. The process according toclaim 2, wherein said viscosity of said starting material in dispersionor solution form is adjustable by adding a gelling agent therein, or byadjusting the temperature thereof.
 8. The process according to claim 7,wherein said gelling agent is selected from the group consisting ofcarbomers, hydroxyethyl cellulose, carboxymethyl cellulose, agar,xanthan gum, starch, polyethylene glycol, polyvinylpyrrolidone, locustbean gum, guar gum, gelatin, casein, pectin, alginates andcarrageenates.
 9. The process according to claim 1, wherein said gradeddroplets have a uniform shape and size.
 10. The process according toclaim 9 wherein said graded droplets have a uniform spherical shape anda size in a range from about 10 μm to about 700 μm.
 11. The processaccording to claim 10 wherein said graded droplets have a uniformspherical shape and a size in a range from about 20 μm to about 100 μm.12. The process according to claim 1, wherein said atomization includesatomization by ultrasonic, acoustic, pressure swirl nozzle, two-fluidnozzle, or electrostatic means.
 13. The process according to claim 1,wherein said controlled freezing rate is at least 200° C. per second.14. The process according to claim 1, wherein said controlled freezingrate is at least 400° C. per second.
 15. The process according to claim1 wherein said freeze-dried granules in a nanoporous anhydrous statehave uniformly sized pores having a pore size less than about 300nanometers.
 16. A detergent composition, comprising freeze-drieddetergent granules prepared according to claim 1 in a nanoporous statehaving uniformly sized pores having a pore size less than about 300nanometers.